Sulphonated higher alcohol esters of the higher fatty acids and method of making the same



Patented May 1, 1934 UNIT STTES SULPHONATED HIGHER ALCOHOL ESTERS OF THE HIGHER FATTY ACIDS AND METHOD OF MAKING THE SALE No Drawing. Application August 22, 193

Serial No. 558,825

14 Claims. (Cl. 260-98) My invention relates to a water-soluble sulphonated higher alcohol ester of the higher fatty acids and to the preparation thereof, and more particularly it relates to a solid or semisolid sulphonated product of wide applicability in the industries, and to the method of manufacturing said product.

One object of my invention is to provide a sulphonated product for use in the industries which is solid or semi-solid at the temperatures encountered in shipping and storing and which product can, therefore, be easily and economically transported and incorporated in and mixed with the various materials in conjunction with which it is employed in the trade.

A further object of my invention is to provide a sulphonated product which forms stable solutions with water containing calcium and magnesium salts as opposed to the sulphonated oils heretofore known which form precipitates with the said metallic salts.

A further object of my invention is to furnish *a sulphonated compound which may be employed in baths containing acid without any tendency 'for the sulphonated product to become waterinsoluble due to hydrolysis as has heretofore been encountered.

Still another object of my invention is to provide a sulphonated product which may be employed in conjunction with the caustic baths of mercerizing processes and with which there will be no salting-out effect on the product, which effect, if encountered as has previously been the case, renders the baths useless if not injurious to the goods treated therein.

Still another object of my invention is to provide a sulphonated product which is miscible in water or aqueous solutions and which, therefore, may advantageously be used in conjunction with baths employed in treating textiles, skins, hides, leather and the like with baths for pickling iron and steel to produce a good standing lather and with water-insoluble organic liquids, such as carbontetrachloride, mineral oil derivatives, and the like, to cause the formation of stable water emulsions therewith.

Other objects, such as the novel method em-- ployed in producing the sulphonated compound of the invention, will be apparent from a consideration of the specification and claims.

The solid or semi-solid sulphonated product of the present invention is applicable for use as an assistant in various textile baths, such as dye, mercerizing, back-filling, boil-off, loading, and carbonizing baths, in which case it acts as wetting-out, dispersing or penetrating agents. It is particularly applicable for use in the dye bath to bring about an even dyeing effect by reason of the uniform and fast penetration brought about by its presence. In the mercerizing bath, the product provides a sufiiciently fast penetra tion of the fibres to cause a reduction in the time of treatment of the fibres with caustic soda. In addition, a well stretched product of high lustre results. Furthermore, the sulphonated compound of the present invention may be used for treating skins, hides or leather to embody greases or fats in these substances in finely dispersed form. It may also be employed as, a foam-producing agent in iron, steel and other metal pickling baths in which case the compound provides a good standing lather. Since the sulphonated product of the present invention is an excellent emulsifying agent for most materials, it may be employed in the preparation of stable, permanent emulsions. It is particularly applicable to bring about wateremulsification of water-insoluble organic liquids, such as carbon tetrachloride, trichlorethylene, mineral oil derivatives, coal tar derivatives and the like.

The sulphonated oils heretofore used or suggested for use in the above applications have inherent disadvantages among which are their tendency to form water-insoluble compounds with the impurities found in the water or with the salts added to the water of the baths, for example, with the calcium or magnesium salts of hard water. Theyalso tend to undergo hydrolysis in acidcontaining baths, thereby becoming water-insoluble. Furthermore, when used in conjunction with caustic soda baths of mercerizing processes, a salting-out efiect on these oils is encountered, making them useless, if not injurious, to the goods treated in these baths. In order to overcome these difliculties, attempts have been made, by complicated methods, to bring about passivation of the active carboxylic group of the sulphonated oils, for example, by the substitution of the amide or amino groups in the compound. It has also been proposed to render the compound less active by increasing the amount of sulpho-acids in the final product. These methods, in addition to the complexities involved, have not given satisfactory products. Furthermore, the sulphonated compounds previously used are liquids at room temperature, and are thus difflcult to handle and to incorporate with the materials with which they are employed in the trade. The compound of the present invention has none of the above recited disadvantages, and is a solid or semi-solid product at the temperatures encountered in -transportation and shippin and in the mms 5 The present lnvention contemplates a sulphonate of a fatty acid and an alcohol, both the fatty acid and the alcohol containing between 10 carbon atoms and 22 carbon atoms. The alcohol and fatty acid may be saturated or unsaturated and the sulphonate may be composed of a group resulting from a saturated fatty acid and a group resulting from an unsaturated alcohol, or vice versa, or both the acid and alcohol may be saturated or unsaturated. The following structural formula: represent the fatty acids and alcohols which may be employed:

Alcohol Acid nHinflOH (saturated) GnH2n+1COOH (saturated). CnHin-IOH (unsaturated) CnH2nlC0Ol'I (unsaturated). CnHn-AOH (unsaturated) CnHEn-JCOOH (unsaturated).

where in the alcohol formulae n equals 10 to 22 and in the acid formulae, as written, n equals 9 to 21, or the total number of carbon atoms in the acid, including the carbon atom of the carboxylic group, equals 10 to 22.

The unsaturated or other alcohols or fatty acids employed may, if desired, be treated in such manner that one or more of the unsaturated groups are satisfied or one or more of the hydrogen groups are substituted by another group. For example, the unsaturated alcohols may contain an aliphatic acid group of not more than four carbon atoms, such as the formyl, acetyl, propionyl, and butyryl group or the compound may be halogenated. It will be thus seen that the invention contemplates such substituted compounds as well as the normal'alcohols and acids. The use of acetylated alcohols and the use of acetylated chlor alcohols are examples of these substituted compounds.

The sulphonate of the present invention results from a sulphonation of one molecule each of the acid and alcohol and its formation and the resulting sulphonate may be designated as an ester sulphonate and may be represented by the following quation:

ester sulphonate+water the sulphonate, the grouping of whichis, therefore, represented by R2 in the above ester .sul-

phona't'e formulaz capric, lauric, myristic, palmitic,v stearic, arachidic, behenic, carnaubic, hypogoeic', oleic', erusic, linoleimand linol'enic; The corresponding alcohclscr other saturated or unsaturated alcohols which containfrom. ten-to twenty-two carbon atoms may be employed, the grouping of which is represented by R1 in the above formula. Some of these are as follows: capryl or dccyl, undecyl, lauryl'or'dodecyl, tridecyl, myristylcetyl or hexadecyl, octodecyl, eikosyl, dodecenyl, hexadecenyl, and octodecenyl. It is to be understood that the above lists are not to be taken as complete, since, as previously pointed out, any normal alcohol or fatty acid which contains from ten to twenty-two carbon atoms may be employed. Obviously also, the sulphonate prepared may be a mixture of sulphonates of various alcohols and fatty acids of the class contemplated. The sulphonates of the fatty acids and alcohols contemplated herein are miscible with water or aqueous solutions, the miscibility depending on the size of the molecule, that is to say the sulphonates with lower carbon content will be more soluble in cold water'than the compounds containing a larger number of carbon atoms, although all the sulphonates contemplated by the present invention will be soluble in Warm or hot water. These sulphonates will form stable aqueous-solutions, as hereinbefore pointed out, which are unaffected by salts, acids or alkalis which may also be present in the solution.

The sulphonates may be formed by any one of a number of processes. For example, it is advantageous in certain instances to employ a wax or other body containing the alcohol and fatty acid in combination and to subject it to a splitting action such as commonly employed to free the alcohol and acid from their combination prior to the sulphonation step. The following examples will be given as illustrative of the processes which may be employed:

Example I 100 kilograms of a mixture containing tetradecyl alcohol and myristic acid in equi-molecular proportions are treated with 25 kilograms of sulphuric acid of 66 Baum at a temperature of or above 20 C. but not exceeding 90 C. until a test shows that the resulting product (the sulphonate) is soluble in a caustic soda solution of 30 Baum. The sulphonate is then washed with 100 kilograms of an aqueous solution containing 5% to 10% of an electrolyte such as Glaubers salt or sodium chloride. solid product (the sulphonate) from the wash water, any excess offree mineral acid is neutralized with any alkaline material.

Example II Spermaceti is treated by one of the well known splitting methods and 50 kilograms of the resulting mixture of alcohols (chiefly hexadecyl alcohol) and fatty acid (chiefly palmitic) are After separation of the dissolved in 20 kilograms of carbon tetrachloride. The solution-is treated with 32 kilograms of; fumingsulphuric acid containing 15% free sulphur trioxide ata temperature of or above'20 'C. but not exceeding. 90 C(until the resulting sulphonateshows upon test that it is soluble in an aqueous.solutioncontaining up to 16% sul phuricacid. The excess-mineral acid is neutralizecl witha suitable reagentlsuch as phosphate and the solvent is then removed wholly or. partially, employing vacuum distillation if 3 desired. a

' Example III 100 kilograms of an equimolecular mixture of treated with 5(l'kilograms of sulphuric acid containing 100% H2SO4 (rnonohydrate) at a temperature of or above 20 C. but notexceeding 90 C. Iron dust or other catalyst' may be added in 145 small percentages. The sulphonation is completed when, upon test, the'product is soluble in a .025% solution of Ca(OH)2. The catalyst is removed by centrifuging and the sulphonate is acetyla'teddodecenyl alcohol and oleic acid are washed with 250 kilograms of a solution of an 15 electrolyte such as an 8% solution of sodium chloride. After separation of the wash water, the excess free mineral acid may be neutralized with any alkaline substance.

It will be noted from the above examples that wide variation is possible in the process of manufacturing the ester sulphonates of the present invention. The process may be carried out in the absence of a solvent or in the presence of an inert solvent such as carbon tetrachloride. A catalyst which is insoluble in the acid used, such as iron dust, may be employed. The acid used may be concentrated or fuming sulphuric acid, or, if desired, chlor-sulphonic acid may be substituted therefor. In the claims, the term acid capable of producing sulphonation includes these acids. It has also been found expedient in certain reactions to form first the chlorinated alcohol or acid before bringing about the sulphonation. For example, the dodecenyl alcohol may be halogenated, for instance chlorinated, to form the chlordodecenyl alcohol which may then be treated with acetic or other anhydride, forming acetylchlordodecenyl alcohol which may then be reacted with the fatty acid and acid capable of producing sulphonation in accordance with any of the methods described. During the sulphonation, hydrochloric acid and Water are split off instead of water alone. The use of these halogenated compounds as well as the use of the untreated alcohols are within the scope of the present invention and fall within the phrase alcohol containing between ten and twenty-two carbon atoms as used herein. When unsaturated alcohols in which at least one of the unsaturated bindings has been satisfied by an aliphatic acid containing not more than four carbon atoms, such as acetylated dodecenyl alcohol, are spoken of in the claims, the number of carbon atoms present in the unsaturated alcohol, say dodecenyl alcohol, is considered and not the number of carbon atoms present in the substituted alcohol.

Other modifications are possible without departing from the essential features of my invention.

I claim:

1. A sulphonated product, suitable for use as an emulsifying, dispersing and penetrating agent, comprising a sulphonate of the formula R1.OSO2.OOCR2 where R1 is a group of a saturated alcohol containing from ten to twenty-two carbon atoms and where OOCRz is a group of a fatty acid containing from ten to twenty-two carbon atoms.

2. A sulphonated product, suitable for use as an emulsifying, dispersing and penetrating agent, comprising a sulphonate of the formula R1.OSO2.OOCR2 where R1 is a group of a satu rated alcohol containing from ten to twenty-two carbon atoms and where OOCRz is a group of a saturated fatty acid containing from ten to twenty-two carbon atoms.

3. A sulphonated product, suitable for use as an emulsifying, dispersing and penetrating agent, comprising a sulphonate of the formula R1.OSO2.OOCR2 where R1 is a group of a saturated alcohol containing from ten to twenty-two carbon atoms and where OOCRz is a group of an unsaturated fatty acid containing from ten to twenty-two carbon atoms.

4. A sulphonated product, suitable for use as an emulsifying, dispersing and penetrating agent, comprising a sulphonate of the formula R1.OSO2.OOCR2 where R1 is a groupof a saturated alcohol in which an unsaturated alcohol containing normally from ten to twenty-two carbon atoms has its unsaturated binding satisfled by an aliphatic acid group containing not more than four carbon atoms and where OOCR2 is a group of a fatty acid containing from ten to twenty-two carbon atoms.

5. The process of making a sulphonated compound which comprises reacting an alcohol containing from ten to twenty-two carbon atoms, a fatty acid containing from ten to twenty-two carbon atoms, and an acid capable of producing sulphonation, and thereafter separating the solid product from the other materials of the reaction.

6. The process of making a sulphonated compound which comprises reacting an alcohol containing from ten to twenty-two carbon atoms, a fatty acid containing from ten to twenty-two carbon atoms, and an acid capable of producing sulphonation at a temperature between 20 C. and 90 C., and thereafter separating the solid product from the other materials of the reaction.

7. The process of making a sulphonated compound. which comprises dissolving an alcohol containing from ten to twenty-two carbon atoms, a fatty acid containing from ten to twenty-two carbon atoms, and an acid capable of producing sulphonation in an inert solvent, allowing a reaction to take place between the compounds, and thereafter removing at least a portion of the solvent.

8. The process of making a sulphonated compound which comprises dissolving an alcohol containing from ten to twenty-two carbon atoms, a fatty acid containing from ten to twenty-two carbon atoms, and an acid capable of producing sulphonation in an inert solvent, allowing a reaction to take place between the compounds at a temperature between 20 C. and 90 0., and thereafter removing at least a portion of the solvent.

9. The process of making a sulphonated compound which comprlses reacting an alcohol containing from ten to twenty-two carbon atoms, a fatty acid containing from ten to twenty-two carbon atoms, and an acid capable of producing sulphonation in the presence of a catalyst which is not dissolved by the acid, and thereafter separating the solid product from the other materials of the reaction.

10. The process of making a sulphonated compound which comprises reacting an alcohol containing from ten to twenty-two carbon atoms, a fatty acid containing from ten to twenty-two carbon atoms, and an acid capable of producing sulphonation at a temperature between 20 C. and 90 C. in the presence of a catalyst which is not dissolved by the acid, and thereafter separating the solid product from the other materials of the reaction.

11. The process of making a sulphonated compound which comprises splitting a wax-like compound consisting of an ester of a fatty acid containing between ten and twenty-two carbon atoms and an alcohol containing between ten and twenty-two carbon atoms into the fatty acid and alcohol respectively, adding an acid capable of producing sulphonation to the mixture of fatty acid and alcohol, allowing a reaction to take place between the fatty acid alcohol and acid capable of sulphonation, and thereafter separating the solid product from the other materials of the reaction.

12. The process of making a sulphonated compound which comprises splitting a wax-like coman emulsifying, dispersing and penetrating agent,

comprising a mixture of sulphonates of the formula R1.OSO2.OOCR2 where R1 is either a satto twenty-two carbon atoms.

urated or an unsaturated alcohol group contain ing from ten to twenty carbon atoms, and where OOCR: is a fatty acid group containing from ten 14. A sulphonated product, suitable for use as an emulsifying, dispersing and penetrating agent, comprising a mixture of sulphonates of the formula R1.OSO2.O0CR2, where R1 is either a saturated or an unsaturated alcohol group containing from ten to twenty carbon atoms, and where 000R: is either a saturated or an unsaturated fatty acid group containing from ten to twenty two carbon atoms.

FRITZ DAMBACHER.

' DISCLAIMER 1,957,324.'Frtiz Dambacher, Chemnitz-Sa., Germany. SULPHONATED HIGHER ALCOHOL ESTERS OF THE HIGHER FATTY Acms AND METHOD or MAKING THE SAME.

Patent dated May 1, 1934. Disclaimer filed July 31, 1934,

by the assignee, E. F. Houghton and Company.

Hereby disclaims:

From claims 5 and 6, any process of making a sulphonated compound in which the alcohol employed in the react1on is not a saturated alcohol.

[Ojicial Gazette August 28, 1.984.]

Certificate of Correction Patent No. 1,957,324.

May 1, 1934.

FRITZ DAMBACHER It is hereby certified that errors appear in the printed specification 0f the above numbered patent requiring correction as follows: Page 2, lines 50 to 52, strike out the equation and insert the following instead Alcohol Sulphuric acid Fatty acid and line 125, for 2O read 200; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case 1n the Patent Oflice.

Signed and sealed this 23rd day of October, A. D. 1934.

[SEAL] LESLIE FRAZER,

Acting Commissioner of Patents.

Certificate of Correction Patent No. 1,957,324. May 1, 1934. FRITZ DAMBACHER It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, lines 50 to 52, strike out the equation and insert the following instead-'- Alcohol -F Sulphuric acid Fatty acid Ester sulphonate and line 125, for 20 read 200; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 23rd day of October, A. D. 1934.

Acting Commissioner of Patents; I 

